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摘要
以双酚AF、氯二硝基苯和碳酸钾为原料,N,N-二甲基甲酰胺(DMF)和甲苯的混合溶液为溶剂,采用加热回流分水法制备2,2-双[4-(2,4-二硝基苯氧基)苯基]六氟丙烷(BDNPFP)。以Pd/C为催化剂,在氢气气氛下,还原BDNPFP,制备2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷(BDAPFP)。通过傅里叶变换红外光谱仪、差示扫描量热仪等对BDNPFP和BDAPFP这2种单体进行了表征。将单体BDAPFP和2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]六氟丙烷(BAPFP-2TF)以不同的比例溶解在N-甲基吡咯烷酮溶液中,并与均苯四甲酸二酐进行缩聚反应,得到黄色的聚酰胺酸溶液,最后通过热亚胺化得到一系列含氟聚酰亚胺薄膜,并对薄膜的热力学性能、光学性能、吸水性和力学性能进行了研究。结果表明:随着单体BDAPFP含量的增加,薄膜的黄度值降低,透光率提高,薄膜的玻璃化转变温度均超过240℃,热稳定性显著增强;薄膜的吸水率均低于3%,疏水性能优异。
Abstract
Using bisphenol AF,chlorodinitrobenzene and potassium carbonate as raw materials,and a mixed solution of N,N-dimethylformamide (DMF) and toluene as the solvent,2,2-bis[4-(2,4-dinitrophenoxy)phenyl]hexafluoropropane (BDNPFP) was prepared by the heating reflux water-separation method.Using Pd/C as the catalyst,BDNPFP was reduced under a hydrogen atmosphere to prepare 2,2-bis[4-(2,4-diamino-phenoxy)phenyl]hexafluoropropane (BDAPFP).The two monomers,BDNPFP and BDAPFP,were characterized by Fourier transform infrared spectrometer and differential scanning calorimeter,etc.The monomer BDAPFP and 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane (BAPFP-2TF) were dissolved in N-methylpyrrolidone solution at different ratios,and a polycondensation reaction was carried out with pyromellitic dianhydride to obtain a yellow polyamic acid solution.Finally,a series of fluorine-containing polyimide films were obtained by thermal imidization,and the thermodynamic properties,optical properties,water absorption and mechanical properties of the films were studied.The results showed that with the increase of the content of monomer BDAPFP,the yellowness value of the film decreased,the light transmittance increased,the glass transition temperature of the film exceeded 240℃,and the thermal stability was significantly enhanced.The water absorption rates of the films were all less than 3%,demonstrating excellent hydrophobic performance.
关键词
BDNPFP
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BDAPFP
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均苯四甲酸二酐
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聚酰胺酸溶液
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含氟聚酰亚胺薄膜
Key words
BDNPFP
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BDAPFP
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phthalic anhydride
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polyamide acid solution
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fluorine-containing polyimide film
含氟聚酰亚胺薄膜的制备及其性能研究[J].
化工新型材料, 2025, 53(11): 150-154 DOI:10.19817/j.cnki.issn1006-3536.2025.11.010
[1] 黄安民,彭军,王进,等.含降冰片低介电透明聚酰亚胺的合成及性能[J].工程塑料应用,2023,51(10):37-43.
[2] 孟祥胜,柯红军,阎敬灵,等.热固性聚酰亚胺树脂研究进展[J].高分子通报,2023,36(8):1027-1041.
[3] 凃思帆,杨丹妮,梁旭昀,等.导热聚酰亚胺及其复合材料的研究进展[J].复合材料学报,2023,40(11):6043-6060.
[4] 李明慧,代梦露,刘凤萍,等.低介电常数聚酰亚胺研究进展:结构与性能的关系[J].高分子通报,2023,36(8):1042-1075.
[5] Yang C,Su Y,Hsu M.Organo-soluble and lightly-colored fluorinated polyimides based on 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride and aromatic bis(ether amine)s bearing pendent trifluoromethyl groups[J].Polymer Journal,2006,38(2):132-144.
[6] Wu Xueliang,Cai Jing,Cheng Yuanrong.Synthesis and characterization of high fluorine-containing polyimides with low-dielectric constant[J].Journal of Applied Polymer Science,2021,139(16):51972.
[7] Lu Zhao,Ma Xiangjun,Huang Qilong,et al.Synthesis of quaternary copolymerized fluorine-containing polyimides with good thermal properties and low dielectric constant[J].High Performance Polymers,2022,34(9):1069-1077.
[8] 王振中,何志斌,任茜,等.基于氧杂蒽含氟二酐单体的聚酰亚胺薄膜的制备与性能研究[J].绝缘材料,2024,57(10):42-52.
[9] 虞鑫海,陈梅芳.2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷型耐高温环氧胶粘剂及其制备方法:中国,201310076575.7[P].2014-08-13.
[10] 项晓青,朱兆璋,刘旦初.钯碳催化剂在硝基还原和碳碳双键加氢反应中的应用[J].复旦学报(自然科学版),1997(1):8-14.
[11] 张丽娟,李四新,虞鑫海.2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]丙烷及其聚酰亚胺薄膜的制备与性能研究[J].绝缘材料,2009,42(6):23-27.
[12] 白帆,江怡雯,李琇廷,等.柔性显示盖板用耐弯折无色透明聚酰亚胺薄膜的制备与性能[J].高分子学报,2024,55(10):1393-1404.
[13] Wu Feng,Zhou Xingping,Yu Xinhai.Synthesis and characte-rization of novel starbranched polyimides derived from 2,2-bis[4-(2,4-diaminophenoxy)pheny l]hexafluoropropane[J].RSC Advances,2017,7:35786-35794.
[14] 宋诗慧,樊立平,胡晓丹,等.含氟聚酰亚胺薄膜的制备及性能研究[J].山东化工,2024,53(11):1-4.
[15] 逄杰.化学亚胺化法制备聚酰亚胺薄膜的研究[D].济南:齐鲁工业大学,2024.
[16] 张婷婷.透明聚酰亚胺薄膜的制备和性能研究[D].延吉:延边大学,2022.
[17] 李恩.含羧基聚酰亚胺环氧导电胶粘剂[D].上海:东华大学,2012.
[18] 张丽娟.含氟亚胺树脂的制备及性能研究[D].上海:东华大学,2010.
[19] 毛蒋莉.聚酰亚胺改性环氧导电胶的研制及其固化动力学研究[D].上海:东华大学,2011.
[20] 李亚东,万传松,虞鑫海.新型防弹环氧胶粘剂的研制与性能研究[J].中国胶粘剂,2024,33(9):41-47.
